Production of halogenated hydrocarbons



Patented Dec. 5, 1950 s mam or HAEOGENATED OCARBONS Louis Schmerllng', Riverside; 111., was to Universal Oil Products corporation of Delaware ompany, Chicago, Ill., a

No Drawing. Application October 31, 1 945 No. 625,950 1': Claims. (Cuzco-$48) This application is a co'ntinuation-in-part of my copending application Serial No. 496,567, now abandoned, filed July 29, 1943.

This invention relates to the condensation of a monohalogenated' saturated hydrocarbon hav- .ing at least '3 carbon atoms per molecule with an olefinic compound selected from-the group consisting of a mono-olefin and a halomono-olefin to produce a halogenatedsaturated hydrocarbon of higher boiling point than said olefinic compound. More specifically, the process is concerned with the condensation of a monohaloalkane or a monohalocyclo alkane and a monoolefinic hydrocarbon orhalomono-olefin in the presence of a boron trifluoride catalyst.

By the term condensation used in this specification and in the claims, I mean the chemical combination of a monohalogenated saturated hydrocarbon and an olefinic compound selected from the group consisting of a mono-olefin and a halomono-oleiin to produce a higher boiling halogen-containing compound with a molecular weight equal to the sum of the molecular weights of said monohalogenated saturated hydrocarbon and olefin or of said monohalogenated saturated hydrocarbon and halomono-olefin.

An object of this invention is to condense a monohalo-alkane and a mono-olefin to forma higher boiling monohalo-alkane.

Another object of this invention is to condense a monohalo-alkane and a mo'nohalomono-plefin to form a dihalo-alkane.

A further object of this invention is to condense a'monohalocyclo-alkane and a mono-olefin in the presence of a boron trifluoride catalyst.

A still further object of this invention is to condense a monohalo-alkane and a cycle-olefin in the presence of a boron trifluoride catalyst.

In one specific embodiment the present inventioncomprises a process for condensing a monohaiogenated saturated hydrocarbon. having at least3 carbon atoms per molecule and a monoolefinic compound selected from the group consisting of a mono-olefin and a halomono-olefln in the presence of a boron trifluoride catalyst to produce a higher boiling halogenated saturated hydrocarbon. V

A- further embodiment of the present invention comprises a process for condens ng a monohaloalkane having at least 3 carbon atoms per molecule and a mono-olefinic compound selected from the group consisting of a mono-olefin and a halomono-olefin in the presence of a boron trifiuoride catalyst to produce a higher boiling halo-alkane. Monohalogenated. saturated hydrocarbons of monochloro-alkanes and monochlorocyclo chlorodecahydronaphtl which react with mono-olefins or'halomono-olefins, according to the process of this invention, haveat least 3 carbon atoms per molecule and including alkyl halides and halocycloparaflins wh ch are also referred to as monchalo-alkanes and monohalocyclo-alkanes, respectively. In general, tertiary halides are more reactive than primary and secondary halides in .these condensation reactions, although primary and secondary halides may also be condensed with mono-olefins and halomono-olefins as herein set forth. While chlorides and-bromides are generally preferred for use in condensation reactions withmono-olefins and halomono-olefins, dfierent alkyl fluorides and iodides and monofluoroand :mono

iodocyclc-alkanes are also utilizable although not necessarily under the same conditions of operation, particularly when diflerent unsaturated compounds such as oleflns and halo-olefins are also involved in the production of various higher molecular weight halogen compounds. Examples alkanes which are especially useful in the process of this invention are tertiary butyl chloride,

tertiary amyl chloride, l-chloro-l-methylcyclopentane, 1-chloro-1-methylcyclohexane, and 9- alene.

' The mono-olefinic .iydrocarbons utilizable in the presentprocess include alkenes and cycloalkenes. These mono-olefins may be either normally gaseous or normally liquid and comprise ethylene, propylene, butylenes, and higher normally liquid olefins, the latter including various polymers of normally gaseous mono-olefins. These alkenes and cyclo-alkenes which are utilizable in the present process may be obtained from any source and particularly from the products of catalyticand thermal cracking of oils, by de-' hydrogenation of parafilnic hydrocarbons, or by the dehydration of. alcohols.

Cyclo-olefinic hydrocarbons useful in the present process comprise cyclic hydrocarbons of the general formula CnHZn-fl in which n represents an integer which is'at least 3 and is preferably 5 or 6. Cyclopentene, alkylcyclopentenes, cyclohexene, and alkylcyclohexenes are the cyclic mono-olefins which I prefer to react with a monohalo-alkane to produce alkylcyclopentyl and alkylcyclohexyl halides including monoalkyl and polyalkylcycloalkyl halides. Thus, a cyclo-olefin and a monohalo-alkane condense to form a monohaloalkyl-cyclo-alkane, while a monoalkylcycloolefin and a monohalo-alkane react to form a monohalodialkylcyclo alkane. Cyclopropene, cy-

clobutene, and alkyl cyclobutenes are. generally halogen atom and one double bon' assaosa more diiiicult to obta n than the cyclo-oleilns containing rings of or 6 carbon atoms and accordingly these cycio-olefins of lower molecular weight are used less frequently in the present process.

Monohalo-olefins which are condensed with monohalogenated saturated hydrocarbons as herein set forth contain one hydrogen atom and one double bond per molecule, and comprise haloethenes, -propenes, -butenes, higher halo-alkenes. Vinyl chloride, allyl chlo- -pentenes, I and ride, allyl bromide, propenyl chloride,and isopropenyl chloride are representative of suitable haloolefins containing one halogen atom 'ami'cnedoi'lble bond per molecule and'utilizable int'the present process. Halo-olefins suitable for the-process rated hydrocarbons and halo-olefins apparently also include halocyclo-olefins '.-.con t a ini ng ,one p Monohalomono-olefins may a be v suitable manner such as by th'ela gen upon an olefin at a'temperatu stitution occurs and substantially n equat ons 1 that at which the principal. reaction is };the-addi v tion of halogen to the olefin'le double They.-

may also be prepared by =thejaddition of a halo'-' e51- gen to an olefinic double form-a 'dihaloalkane from which one'ii'fiilji.(ill 1 1.v bifoportionpf hydrogen halide may be removedbyfafny of s v eral well known methods to produce'a monohalo-- mono-o1efln. Furthermore, monohalomonooiefins may be prepared by addition of a hydrogen halide'to an acetylenic hydrocarbon.

Dichloroethylene, dichloropropene, and other polyhalomono-olefins are also utilizable in my process for condensing with a monohalo-alkane or monohalocyclo-alkane.

The boron trifluoride catalyst employed in the process of this invention has the advantage over a metal halide catalyst of'the Friedel-Crafts type, which I have also found may be used for assisting condensations of the types herein de scribed, in that boron trifiuoride is a gas and is sufiiciently soluble in the alkyl halide or halocycloparafiin to permit a practically homogeneous reaction. Furthermore, alkyl halides such as tertiary butyl chloride are quite stable in the presence of boron trifluoride as evidenced by the fact that more than 90% of tertiary butyl chloride was recovered from the product obtained ,by saturating tertiary butyl chloride with boron trifluoride at 8 C. and permitting the solution to stand at that temperature for 2 hours. Also, alkyl fluorides, e. g.. tertiary butyl fluoride may be condensed with olefins and'halo-olefins in the presence of catalytic amounts of boron fluoride Tertiary butyl chloride undergoes similar condensations with propylene and with n-butylenes producing chloroheptane and chloro-octane, respectively. Similarly. bromoheptane may be obinvolve the additionof the former to the double bond of the halo-olefin to produce a halo-alkane with a molecular weight equal to the sum of the ,molecular weights of. the two reactants. For exjample, the condensation of tertiary butyl chloride and vinyl chloride produces 1,1-dichloro-3,3-

dimethylbutane which is a dichloroneohexane. This reaction is illustrated by the following (cm) accl+mc=crrc1 mmnccmcnch The dichlorohexane indicated in the preceding equation may be converted into neohexane, tertiarybutyl acetaldehyde, 'chlorohexene, or other desirable compounds. The process of this invention thus teaches a simple method for preparing compounds containing a quaternary carbion" atom as well as of homologs of vinyl chlor de.

The condensation of a monohalogenated saturated hydrocarbon and a mono-oleiinic compound selected from the group consisting of a mono-olefin and a halomono-olefin is carried out by contacting these reactants in the presence of boron triiiuoride at a temperature of from about -1 0 to about 100 C. but preferably at a temperature of from about 10 to about 50 0., when a tertiary butyl halide is present and while maintaining a pressure suificient to keep in liquid state a substantial proportion of the reaction mixture. The condensation of different monohalo-alkanes and monohalocyclo-alkanes with different mono-olefins and halomono-olefins are not necessarily carried out with equal ease nor at the same conditions of operation.

The reaction of a monohalogenated saturated hydrocarbon with an olefin or halo-olefin may be carried out in the presence of a boron trifiuoride catalystin either batch or continuous types of operation. In match type operation, desired proportions of monohalo-alkane and a mono-olefin or monohalo-alkane and a halo-olefin are introduced to a suitable reactor together with a boron trifluoride catalyst, and the resultant commingled materials are contacted at a reaction temperature until a substantial proportion of the reactants is converted into the desired higher molecular weight halogenated hydrocarbon. The reaction mixture, after separation from the catalyst, is fractionated to separate the unconverted monohalogenated saturated hydrocarbon and olefin or halo-olefin from the higher boiling halogenated hydrocarbon reaction product, and the recovered materials may then be used in another run to produce an additional quantity of the desired halogenated hydrocarbon.

Continuous operations may be carried out by conducting a mixture of a monohalogenated saturated hydrocarbon and a mono-olefin or halomono-olefin through a reactor of suitable design in the presence of boron trifiuoride. In this type of treatment, the operating conditions may be adjusted suitably, and may difl'er somewhat from those employed in batch type operation.

In some cases it may be advisable to commingle the charged monohalo-alkane or monohalocycloalkane and monoolefln or halomono-olefln with a substantially inert solvent .such as a parafllnic hydrocarbon, for example, normal pentane, and then to eilect condensation in the presence of this added solvent and of the boron trifluoride catalyst. Obviously the solvent chosen should be one which does not undergo undesirable reactions with the other components of the reaction mixture under the operating conditions of the reaction.

Diiierent higher boiling halogenated hydrocarbons produced by the present process may be used for various purposes. Some of them may be converted into hydrocarbons of high antiknock value, others may be used as solvents or employed as intermediate compounds in organic syntheses.

The following examples are given to illustrate the character of results obtained by the use of the present process, although the data presented are not introduced with the intention of unduly restricting the generally broad scope of the invention.

Example I Condensation of tertiary butyl chloride with propylene took place in excellent yield when 26 grams of this olefin were passed at C. during a period of forty minutes into a solution of 8 grams of boron trifluoride in 100 grams of tertiary butyl chloride. The principal product was 49 grams of a chloroheptane (B; P. 125-135 C.; n 1.4275 consisting mainly of 4-chloro-2,2-dimethylpentane- Example II The condensation of tertiary butyl chloride with ethylene took place in the presence of boron trifluoride at room temperature. This reaction was carried out as a batch operation in a rotating autoclave to which 50 grams of tertiary butyl chloride and 4 grams of boron trifluoride were charged, and ethylene was pressed into a pressure of 40 atmospheres after which the autoclave was rotated at room temperature for four hours. It was then allowed to set overnight before being opened. There was obtained 16 grams of chlorohexane (B. P. 115-120 C.) as well as 8 grams of chloro-octane and a substantial amount of other secondary products.

Example III Isopropyl chloride was reacted with ethylene at 70 C. in a rotatable steel autoclave in a manner similar to that used in Example 11. The principal product was a chloroheptane, namely 1- chloro, 3,3-dimethylpentane (B. P., 148-l50 C.) and not a chloropentane. The formation of the chloroheptane apparently involved the reaction of one molecular proportion of isopropyl chloride with two molecular proportions of ethylene. In this reaction it is presumed that an amyl chloride was formed-first by the condensation of equal molecular proportions of isopropyl chloride and ethylene, and that the amyl chloride then reacted with an additional molecular proportion of ethylene to yield the chloroheptane.

Example IV Boron trifluoride was passed slowly into a. soluthe solution was saturated, when about 3 grams of boron trifluoride was absorbed. The reaction mixture was permitted to stand at 0 C. for 20 hours after which the clear, dark red liquid product was decanted from 3 grams of sludge and was then washed with water, dilute alkali and water, and was then dried and distilled. Besides unreacted tertiary butyl chloride and 07010- hexene, this reaction mixture contained about 8 grams of chlorocyclohexane. 8 grams of tertiary butyl cyclohexene. and 15 grams oi chlorotertlary butyl cyclohexane having'a boiling point of 86-88 C. at 8 mm. pressure (215-216 C. at atmospheric pressure), a melting point of -10 C., and a refractive index, 11 of 1.4790.

Of these diii'erent reaction products, the chlorotertiary butyl cyclohexane resulted from the condensation of tertiary butyl chloride and cyclohexene. while the tertiary butyl cyclohexene was formed by dehydrochlorination oi chlorobutyl cyclohexane, and the hydrogen chloride resulting from this dehydrochlorination added to cyclohexene to give the chlorocyclohexane.

It is significant that the chlorobutyl cyclohexane which I obtained in the presence of the boron trifluoride catalyst is difl'erent from that obtained when aluminum chloride is the catalyst. Chlorobutyl cyclohexane formed in the presence of aluminum chloride catalyst does not crystallize even when cooled to 78 C., its refractive index at 20 C. is 1.4690, and its infrared spectrum is markedly diflerent from that of the chlorobutyl cyclohexane produced by my process in the presence oi boron trifluoride. I have found that 1- chloro-l-tertiary butylcyclohexane is formed in the presence 0! boron trifluoride, while a mixture of 1-chloro-1-tertiary butylcyclohexane and 1- chloro-3-tertiary butylcyclohexane is produced in the presence of an aluminum chloride catalyst.

Example V temperature for four hours, allowed to stand overnight, and then opened. Distillation oi. the liquid product yielded 108 grams oi. 1,1-dichloro-3.3-dimethylbutane with B. P. 147-148 C., M. P. 60 C., and uh", 1.4399.

The same dichloroneohexane, namely 1,1-dichloro-3,3-dimethylbutane, is obtained, but iniower yield by the reaction of isobutyl chloride with vinyl chloride.

Example VI 1-fluo-3,3-dimethylbutane (B. P., 75-76 C.; a 1.3732; d4" 0.7818; identified by hydrolysis to 3,3-dimethylbutanol) is obtained in good yieldby the reaction of 50 grams of tertiary butyl'fluoride with ethylene in the presence of 3 grams of" boron trifluoride using the proceduce of Example II.

The foregoing specification and examples illustrate the novelty and utility oi the present invention, although neither section is introduced with the intention of unduly limiting its generally broad scope.

I claim as my invention:

1. A process which comprises reacting a monohalogenated saturated hydrocarbon having at least 3 carbon atoms per molecule with a monooleiinic compound selected from the group consisting of a mono-olefin hydrocarbon and a haloabout 100 C. and a pressure suflicient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a higher boiling halogenated saturated hydrocarbon having a molecular weight equal to the sum of the molecular weights of the reactants and recovering said higher boiling halogenated saturated hydrocarbon.

2. A process which comprises reacting a monohaloalkane having at least 3 carbon atoms per molecule with a mono-oleflnic compound selected from the group consisting of a mono-olefin and a halomono-olefln hydrocarbon in the presence of a boron trifluoride catalyst at a temperature of from about 10 C. to about 100 C. and a pressure suilicient to maintain a substantial proportion of the reactants in liquid state, whereby to produce-a higher boiling halo-alkane having a molecular weight equal to the sum of the molecular weights of the reactants and recovering said higher boiling halo-alkane.

3. A process which comprises reacting a primary monohalo-alkane having at least 3 carbon atoms per molecule with a mono-oleflnic compound selected from the group consisting of a mono-olefin hydrocarbon and a halomono-olefln in the presence of a boron trifluoride catalyst at a temperature of from about 10 C. to about 100 C. and a pressure sufiicient to maintain a substantial proportion of the reactance in liquid state, wherebyto produce a higher boiling haloalkane having a molecular weight equal to the sum of the molecular weights or the reactants and recovering said higher boiling halo-alkane.

4. A process which comprises reacting a secondary monohalo-alkane with a mono-olefinic compound selected from the group consisting of a mono-olefin hydrocarbon and a halomonoolefin in the presence of a boron trifluoride catalyst at a temperature of from about l C. to about 100 C. and a pressure suflicient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a higher boiling halo-alkane having a molecular weight equal to the sum of the molecular weights of the reactants and recovering said higher boiling halo-alkane.

5. A process which comprises reacting a tertiary monohalo-alkane with a mono-olefinic compound selected from the group consisting of a monoolefin hydrocarbon and a halomono-olefin in the presence of a boron trifluoride catalyst at a temperature of from about l0 C. to about 100 C. and a pressure suflicient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a higher boiling halo-alkane having a molecular weight equal to the sum of the molecular weights of the reactants and recovering said higher boiling halo-alkane.

6. A process which comprises reacting a monohalo-cyclo-alkane with a mono-olefinic compound selected from the group consisting of a monoolefin hydrocarbon and a halomono-olefin in the.

presence of a boron trifluoride catalyst at a temperature of from about l0 C. to about 100 C. and a pressure suflicient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a higher boiling halo-cycloalkane having a molecular weight equal to the sum of the molecular weights of the reactants and recovering said higher boiling halocycloalkane.

7. A process which comprises reacting a tertiary monohalocyclo-alkane with a mono-oleilnic compound selected from the group consisting oi a mono-olefin hydrocarbon and a halomono-oleiln in the presence of a boron trifluoride catalyst at a temperature oi from about 10 C. to about C. and a pressure sufficient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a higher boiling halocycloalkane having a molecular weight equal to the sum oi the molecular weights of the reactants and recovering said higher boiling halocycloalkane.

8. A process which comprises reacting a monochlorinated saturated hydrocarbon having at least 3 carbon atoms per molecule with a mono-olefin hydrocarbon in the presence 01 a boron trifluoride catalyst at a temperature 01' from about --10 C. to about 100 C. and a pressure suflicient to maintain a substantial proportion 01' the reactants in liquid state, whereby to produce a higher boiling chlorinated saturated hydrocarbon having a molecular weight equal to the sum of the molecular weights of the reactants and recovering said higher boiling chlorinated saturated hydrocarbon.

9. A process which comprises reacting a monochloro-alkane having at least 3 carbon atoms per molecule with a mono-olefin hydrocarbon in the presence of a boron trifluoride catalyst at a temperature of from about 10 C. to about 100 C. and a pressure suiheient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a higher boiling chloro-alkane having a molecular weight equal to the sum of the molecular weights of the reactants and recovering said higher boiling chloro-alkane.

10. A process which comprises reacting a monochlorocyclo-alkane with a mono-olefin hydrocarbon in the presence of a boron trifluoride catalyst at a temperature of from about 10 C. to about 100 C. and a pressure sufl'icient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a higher boiling chlorocyclo-alkane having a molecular weight equal to the sum of the molecular weights of the reactants and recovering said higher boiling chlorocycloalkane.

11. A process which comprises reacting a monochloro-butane with a mono-olefin hydrocarbon in the presence of a boron trifluoride catalyst at a temperature of from about 10 C. to about 100 C. and a pressure suflicient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a higher boiling chloroal'kane having a molecular weight equal to the sum of the molecular weights oi. the reactants and recovering said higher boiling chloro-alkane.

12. A process which comprises reacting a tertiary butyl halide with a mono-olefin hydrocarbon in the presence of a boron trifluoride catalyst at a temperature of from about 10 C. to about 50 C. and a pressure suihcient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a higher boiling haloalkane having a molecular weight equal to the sum of the molecular weights of the reactants and recovering said higher boiling halo-alkane.

13. A process which comprises reacting tertiary butyl chloride with a mono-olefin hydrocarbon in the presence of a boron trifluoride catalyst at a temperature of from about l0 C. to about 50 C. and a pressure sufllcient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a higher boiling chloro-alkane having a molecular weight equal to the sum of the molecular weights of the reactants and recovering said higher boiling chloro-alkane.

14. A process which comprises reacting tertiary butyl chloride with ethylene in the presence of a boron trifluoride catalyst at a temperature of from about -10 C. to about 50 C. and a pressure suflicient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a chloroneohexane and recovering the last-named compound.

15. A process which comprises reacting tertiary butyl chloride with cyclohexane in the presence of a. boron trifluoride catalyst at a temperature of from about 10 C. to about 50 C. and a pressure suflicient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a chlorotertiary butyl cyclohexane and recovering-the last-named compound.

16. A process which comprises reacting tertiary butyl chloride with a monochloromono-olefin in 20 the presence of a boron trifluoride catalyst at a temperature or from about 10 C. to about 50 C. and a pressure sumcient to maintain a substantial proportion of the reactants in liquid state,

whereby to produce a dichloro-alkane having a molecular weight equal to the sum of the molecular, weights oi. the reactants and recovering said dichloro-alkane.

17. A process which comprises reacting tertiary butyl chloride with vinyl chloride in the presence of a boron trifluoride catalyst at a temperature of from about -10 C. to about 50 C. and a pressure sufflcient to maintain a substantial proportion of the reactants in liquid state, whereby to produce a dichlorohexane and recovering the last-named compound.

LOUIS SCHMERLING.

10 REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,068,772 Sixt Jan. 26, 1937 2,246,762 Schirm July 24, 1941 2,297,564 Kirkbride Sept. 29, 1942 2,399,512 Schmerling Apr. 30, 1946 FOREIGN PATENTS Number Country Date 261,689 Germany July 2, 1913 695,125 France Dec. 11, 1930 824,909 France Feb. 18, 1938 OTHER REFERENCES Henne: Jour. Am. Chem. Soc., vol. 60, pages 1697, 2491 (1938).

Simons et al.: Ibid, vol. 60, pages 2956-7 (1938).

Simons et al.: Industrial and Engineering Chemistry," vol. 32, pages 178-80 (1940) Nenitzescu et al.: Ber. der Deut. Chem. GeselL," vol. 693, pages 2706-7 (1936) Nenitzescu et al.: Annalen der Chemie," vol. 519, page 267 (1935).

Truflault: Comptes Rendus," vol. 202, pages 1286-7 (1936) Simons et al.: "Jour. Am. Chem. 800.," vol. 65, pages 1269-1271 (1943). 

1. A PROCESS WHICH COMPRISES REACTING A MONOHALOGENATED SATURATED HYDROCARBON HAVING AT LEAST 3 CARBON ATOMS PER MOLECULE WITH A MONOOLEFINIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF A MONO-OLEFIN HYDROCARBON AND A HALOMONO-OLEFIN IN THE PRESENCE OF A BORON TRIBLUORIDE CATALYST AT A TEMPERATURE OF FROM ABUT -10*C. TO ABUT 100*C. AND A PRESSURE SUFFICIENT TO MAINTAIN A SUBSTANTIAL PROPORTION OF THE REACTANTS IN LIQUID STATE, WHEREBY TO PRODUCE A HIGHER BOILDING HALOGENATED SATURATED HYDROCARBON HAVING A MOLECULAR WEIGHT EQUAL TO THE SUM OF THE MOLECULAR WEIGHTS OF THE REACTANTS AND RECOVERING SAID HIGHER BOILING HALOGENATED SATURATED HYDROCARBON. 